Process and apparatus for reducing unsaturated materials.



A. H. NvEY.

PROCESS AND APPARATUS FOR REDUCING UNSATURATED MATERIALS.

APPLICATION FILED JuNE |512.

l l 85,704. Patented June 6, 1916.

UNTTED sTATEs PATENT oEEIcE.

ADOLPHUS HENRY NEY, OF HASBEOUCK HEIGHTS, NEW JERSEY, ASSIG-NOR, BY IVLESN'E' ASSIGNMENTS, T0 HYDROGENATED OIL COMPANY, OF NEW YORK,4 N'. Y., A COR- PORATION OF NEW YORK.

PROCESS AND APPARATUS FOR REDUCIN'G UN SATURATED `1\t[A'.l.EIR.[ALS.

*Specification of Letters Patent.

Patented June 6, 1916.

lApplication led J' une 7, 1912. Serial No.' 702,367.

To all 'whom 'it may concern.'

Be it known that I, ADoLPHUs HENRY NEY, a resident of the United States, who has declared his intention to become a citilZen thereof, of Hasbrouck Heights, in the county of Bergen and State of New Jersey, have invented certain new and useful Improvements in Processes and Apparatus for Reducing Unsaturated Materials, of which the following is a specification.

This invention relates to a process of hydrogenating oils, and relates in particular to the method of treating glycerids and similar oily bodies containing unsaturated compounds, with hydrogen gas or other gaseous mediums containing hydrogen or similar reducing material in the presence of nickel or other catalyzers, as well as to an apparatus suitable for carrying out said process, all as hereinafter particularly described and claimed.

The generally accepted theory for the eX- planation of the catalytic reactions is the formation of certain unstable intermediate compounds of the catalyst with one or more of the reagents. In the instance of the catalysts, like nickel, the formation and decomposition alternate of a nickel-hydrogen compound or hydrid is hypothetically presumed. It is immaterial for the purpose of the present consideration whether these hydrids are stable for any length of time under certain conditions or whether they always instantaneously are formed, decompose and are reformed. In the technical application of catalytic reduction the fact alone is of importance that under certain favorable conditions the formation of the hydrid takes place and subsequently an eX- change or transfer of -the hydrogen atom from the hydrid tothe organic body. In considering the dynamics of this reaction it is apparent,that. the-hydrogenation of organic bodies must take place 1n a series of distinct phases. When the organic body rst comes in contact with prepared catalyst in the presence of hydrogen, an instantaneous transfer of the stock of hydrogen already present in the catalyst takes place. Subsequently if the catalyst is again exposed to the influence of a fresh supply of hydrogen a reformation or regeneration of hydrid follows, followed by a renewed transfer of hydrogen to fresh material until all unsaturated bodies have become saturated ones. It is however clear that this is only the case if the catalyzer is permanently kept free of the organic material or where the organic body can be maintained in form of a true vapor or gas under the conditions of hydrogenation.

. In case of organic material incapable of being transformed into the vaporous or gaseous state, entirely differentl conditions prevail. lWhen the material, such as a mixture of the glycerids of unsaturated fatty acids, meet first the catalyzer, the first of the above mentioned phases takes place. However, as the hydrogenated material and the excess of-the original product keep on flowing over the catalyzer or reaching it in some other way, .these bodies are not immethus preventing or greatly impeding the re- .l A

formation of the hydrid due to the sealing up of the surfaces of the catalyst and pre- Venting the access of the hydrogen to it.

like this exist under all the methods at present proposed for a technical execution of the hydrogenation process, and obviously this dificulty must to an extent, always eXist in case of the'hydrogenation of certain compounds, like oils and fats, as it is commercially unfeasible to bring these bodies into the state of a-true vapor or gas.

It has been proposed heretofore to treat oils with hydrogen in the presence of catalyzers, by the process ,ofl agitating the oil in the presence .of said catalyzers and hydrogen gas, or even bythe method of allowing the oil to How past or through a mass of stationary catalyzer in the presence of hydrogen under'` certain conditions. These methods do not take sufficiently into consideration thel fact that' the viscosity, etc., of the oil causes the catalyzer toi be covered with a substantially impervious film, which In a greater or lesser measure conditions nuded o-f any substantial film of saturated spect to hydrogen.

in a large measure, prevents access of hydrogen to the catalyzer,"and therefore` prevents the rapid union of the hydrogen with the.unsaturated body. ln further explanation of this condition, it briefly may be stated that when a catalyzer, such for 'eX- ,ample as nickel, reduced from the oXid by hydrogen gas, is first treated with an. oil, the combined hydrogen which is perhaps present as the hydrid, is taken up by the oil leaving the catalyzer impoverished with re- Moreover, the catalyzer is at this time coated with the oil and therefore sealed away from the hydrogen atmosphere, so that the gas no longer has access to it. Therefore the hydrid, which is the body apparently acting to reduce or saturate the. unsaturated bodies, is no longer capable of formation. A

The present invention has for its object the treatment of the catalyzer or the coordination of the two operations of contacting the oily material and an elastic fluid such as steam with the catalyzer in such a manner that the latter is constantly deoil, and thereby rendered continuously active (or revivified) by the constant reformationof the active hydrid material.

By reference .t0 the accompanying illustrative drawings, it will be seen in what manner an embodiment of the invention may be carried out. v

lin the accompanying drawings, which are purely diagrammatic, Figures 1 and 2 show vertical sections -of a treating chamber.l Fig. 3 is a detail section of an improved formof the atomizer nozzle.

ln the drawings, 1 is a chamber ha-ving a steam inlet pipe 2, and an oil inlet pipe 3 and mixing cap 15 l(or preferably a plurality of such); The discharge ends of these' pipes, sshown-in Fig. 3, are arranged to produce a complete atomizationof the oil, reducing it to a fog.

4 is an inlet pipe for/supplying hydrogen to the-chamber, and 5 is an outlet pipe for the removal of the spent gases.

6 is a mass of catalytic material such as reduced nickel, copper, iron, cerium, palladium, platinum and their oXids or salts according to circumstances. The catalyzer is Y preferably arranged in a plurality of layers or series of baskets as shown in Fig. 1.

7 is a chamber placed beneath the treat; ingv tank 1, to receive the hydrogenated oil, and connected to the chamber 1, by the pipe 8.

9 is an exhaust pipe, connected with the receiving chamber 7, which may be used to produce a partial vacuum in the chamber 7 as desired. ln Fig. 2, the steam or other atomizing fluid and oil inlet pipes 2 and 3 are shownin multiple, so as to produce a plurality of atomizing jets. The hydrogen nieuwe inlets and outlets are shown as 4 and 5- respectively. In this case, the catalyzer is placed in a drum 10,. which is capable of being rotated by the gears 17, and which is made of some porous materlal, such as wire netting or the like, as shown at 14, and the atomized oil, or oil fog, is allowed to impinge, from the stationary atomizers 16, at a definite velocity, upon the catalyzer held in place, by the foraminous periphery of the drum, which velocity is adjusted with respect to the speed of revolution of the drum, so as to produce any desired degree of impregnation of catalyzer by the fog, or atomized oil. rlhe speed may, however, be so regulated that the oil-fog penetrates only a moderately short distance beneath the peripheral surface of the drum, and is then ejected by centrifugal force, the oil being in a non-vaporized or liquid state (the catalyzer of course, being maintained below the boilingor-decomposing point of the product). This operation produces a novel action of extreme importance, fo-r owing to vthat while the catalyzer is freely in contact` with the fog particles in the presence of the hydrogen gas, the discrete or'concrete particles of oil areremoved from its surfaces `by centrifugal action, and thereby the catalyzer is revivified or prevented from becoming sealed away from the hydrogen gas, and its action upon the oil is constant and effective. Thus, the reformation of the hydrids (or other action produced by the contactof the catalyzer and hydrogen), is continually in progress. A catalyzer of substantially constant hydrogen (or hydrid) content is secured, and the uncertain'operation of the methods heretofore practiced as above recited, does not obtain.

lin Fig. 2, 12 4and steam injecting pipes respectively, whereby if desired, the oil fog may be enteredinto the interior of the catalyzer drum, so that the fog has to penetrate from the center of the drum to the periphery. The oil is finely divided or converted into an oil fog by the atomizing action of the atomizing fluid issuing within, and concentric with the jet of oil. This action continues at a predetermined rate so long as the oil remains in the state of a fog, so that the necessary time contact or time factor, of the oil with the catalyzer is secured, while the oilwhich condenses or agglomerates to a discrete or concrete form, is quickly ejected through the porous walls of the drum.

lill@ 13 representyoil and llLE In the above described apparatus, when using nickel as a catalyzer, it is preferable to have the container of nickel, or suitably nickel coated if of iron or steel, as iron in the presence of nickel sometimes shows a tendency toward anticatalytic action.

What I claim is 1. The process of treating oily materials containing unsaturated bodies, which comprises forming said oily materials into an atomized condition, and bringing the oil fog thereby produced into Contact with hydrogen and a freely porous catalytic body, constantly maintained substantially free from a sealing coat of oil.

l 2. The process of treating oily materials containing unsaturated bodies, which comprises forming s'aid oily materials into an atomized condition, bringingthe same into shifting contact with hydrogen and a porous catalytic body, constantly maintained substantially free from a sealing coatv of saturated oil, and removing said oily material in a non-atomized state from said catalyzer.

8. The process of treating oily materials containing unsaturated fatty bodies, which comprises forming said oily materials into an atomized condition, and bringing the same into shifting contact with a moving catalytic body constituting a freely permeable bed constantly maintained substantially free from a sealing coat of saturated oil, and whose interior surfaces are in f ree contact with hydrogen. v

4. The process of treating oily materials containing unsaturated bodies, which comprises forming said oily material into an atomized condition, and in the presence of hydrogen-containing gas, bringing the atomized oil into contact with a porous catalytic body, maintained substantially free froma sealing coat of saturated oil.

5. A process of treating oily material containing unsaturated bodies which comprises atomizing said oily materials, and passing the same through a penetrable mass containing a catalytic agent maintained substantially free rom a scaling coat of saturated oil, and allowing hydrogen to contact with said catalytic agent.

6. A process of hydrogenating oil, which comprises continuously supplying `oil and hydrogen into contact with a catalyzer, thereby causing the reduction of the oil, maintaining said catalyzer substantially free from a sealmg coat of hydrogenated oil and continuously revivifying the catalyzer, and withdrawing the hydrogenated product,

- from the catalyzer in a liquid state.

7. A process of hydrogenating oil, which comprises supplying oil in an atomized condition and hydrogen to a closed chamber, passing the oil through a catalyzing material carried by a fora-minous member pervious to oil and hydrogen and impervious to said catalytic material and withdrawing the hydrogenated product, while maintaining at least the major portion of the catalyzing material at a temperature below the boiling point of the product. v

8. A process of hydrogenating oil which comprises atomizing oil, continuously passing at least. one portion of the said atomized oil through a catalyzer in one direction while providing contact between at least a portion of said catalyzer and hydrogen to reduce the oil, and immediately and continuously passing in the same direction, the reduced product of said portion of oil through a foraminous member in contact with saidcatalyzer, said member being pervious to oil and hydrogen but impervious to the catalyzer, to separate the hydrogenated oil and the catalyzer from each other.

v9. In the hydrogenationof oil the herein described step which comprises atomizing an oil containing unsaturated bodies into contact with a moving catalyzer carried by a foraminous member through which oil and hydrogen can pass, but through which the catalyzer can not readily pass, removing the hydrogenated oil directly from the catalyzer through said foraminous member, constantly revivifying said catalyzer, and maintaining hydrogen in contact with at least aportion thereof coming from a given atomizer continuously in vone vdirection through a retain. ing device pervious thereto, containing-a catalyzer to which it is impervious, and provid ing contact between at least a portion of said catalyzer and hydrogen, while maintaining at least the major portion of said catalyzer at a temperature below the boiling point of the product.

12. An apparatus for hydrogenating yoil comprising a chamber, a structure therein comprising a catalyst and a material pervious to oil and hydrogen, but not pervious to the catalyst, means by .Which the oil may be forced through said catalyst and said pervious material, while in contact with an atmosphere containing free hydrogen, a hydrogen inlet to said chamber, and an atomizer forv directing the oil against said structure.

13.1A process of hydrogenating oil which comprises atomizing oil, passing said at- .omized oil into contact with and through a l comprises sustaining a catalyzing material within a foramlnous supporting member impervious to said material but pervious to'- oil and hydrogen and continuously passing oil in an attenuated condition throughsaid catalyzer and said member, while at least a portion of said catalyzer is in the presence of hydrogen, to reduce said oil, while maintaining at least the major portion of the catalyzer below the boiling point of the product.

16. A process of hydrogenating oil, which comprises forcing oil in an atomized, finely divided condition, through a mass of catalyzing material, at least a portion of which is in the presence of hydrogen, andl thereby reducing the oill without mixing the catalyzer with the product, and maintaining at least the major portion of said catalyzing material at a temperature below the boiling point of the product.

17. An apparatus for hydrogenating oil comprising a closed casing having a body. of catalyst therein, a plurality of pipes eX- tending into the chamber formed lby said casing, a nozzle on a plurality of adjacent pipes for atomizing the oil, means for rotating the said body of catalyst relatively to the said nozzle, and areceptacle pervious t0 oil and hydrogen, but, impervious to catalyst,`for retaining the catalyst.

18. A process of hydrogenating oil, which Acomprises continuously atomizing oil, continuously passing the atomized oil, while at least a portion thereof is in the presence of free hydrogen, through a catalyzing material confined'. within f material impervious t0 the catalyzing material and pervious to oil and hydrogen to reduce the oil, and withdrawing the hydrogenated product.

19. A process of hydrogenating oil which comprises continuously supplying and atomizing oil, continuously passing the resulting atomized oil toward and through a catalyzing material confined against admixture with the product while at least a por tion of said catalyzing material 1s 1n the f presence of hydrogen.

20. A process of hydrogenating oil whichcomprises introducing oil under. pressure into a chamber, atomizing the oil therein,

forcing the atomized loil through a catalyzer a portion at least of which is in the prcesence of hydrogen, withdrawing the hyinto contact with a catalyzer so drawing the hydrogenated product said chamber.

- comprising a Licence drogenated product from the chamber, and

maintaining at least the major portion of the catalyzer at a temperature vbelow the volatilizing point of the product.

21. A process of hydrogenating oil which comprises separately introducing hydrogen and oil under pressure into a chamber, atomizing the oil, forcing the atomized oil into contact with and through a mass yof catalyzing material, at least a portion of which is in the presence of hydrogen, said material being held in a support impervious thereto but pervious to oil and hydrogen.

22'. The hereinl described process of hydrogenating oil, which comprises continuously directing a flowing current of 'atomized oil in a closed chamber upon a body comprising. a catalyzing material held by a material impervious thereto, forcing the oil through said catalyzing material and said material impervious thereto while a portion of said catalyzing material is in the presence of hydrogen, and withdrawing the'hydrogenated product from said chamber, and maintaining a temperature in the reacting chamber below the vaporizing point of the product.

23. The herein described process of hydrogenating oil which comprisesl directing a flowing current containing atomized oil in a closed chamber upon successive portions of the surface of a structure containing a catalyst held within a retaining material impervious thereto but pervious to oil and hydrogen, thereby bringing said oil in contact with successive portions of said catalyst, and into contact with and through said retaining material while at leastv a portion of said catalyst is in the presence of hydrogen, continuously withdrawing the hydrogenated product from contact with the catalyst within the closed chamber below the vaporizing point of the product.

24. The herein described process of removing films of oil from a catalyzer which comprises subjecting said catalyzerto centrifugal force sufficient to throw out drops `of oil from said catalyzer, while directing steam against said catalyzer.

25. The herein described process, which consists in first atomizing a stream of oil into a mist without gasification', while in a closed chamber, then bringing such mist confined that oil may pass through without carrying the catalyzer, tween hydrogen andv at least a part of'said oil, whereby the oil is reduced, and githrom 26. vA proccssof comprises passing foil through va structirre foraminous supporting member carrying catalytic materi l, said memand maintaining a temperature while providing contact behydrogenating oil which i ber-being pervious to oil and hydrogen, but i impervious to said catalytic material, while at least a portion of said catalytic material is in the presence of hydrogen, and below the vaporizing point of the product.

27. A process of hydrogenating oil which comprises' continuously atomizing oil, continuously kpassing-the atomized oil while at, least a portion thereof is in the' presence of free hydrogen, through a catalyzing material confined within a container impervious to the catalyzing-material but lpervious to oil and hydrogen to reduce the .oil, withdrawing the hydrogenated product from contact with the said catalyzing material, and maintaining at least the major portion of the vcatalyzing material at a temperature below the boiling'point of the product.

28. An apparatus -for hydrogenating oil comprising a closed chamber, .a catalyzing vmaterial placed 'therewithim 'and a v'retainer impervious vto said material' surrounding the i same, at least a part of which is pervious to oil and hydrogen, and means for atomiz ing the oil and for directing the saidl atomized oil into. contact with and through said catalyzing 4material, and a hydrogen inlet for said chamber. v

29.- An apparatus for hydrogenating oil comprising a closed casing, 'a pervious v catalyzing material, `means for moving the catalyzing material and the nozzles relative to each other, said casing fbeing provided with a hydrogeninlet.- f 4 30. An apparatus for hydrogenatingk-ail comprising a closed casing, a pervious body of catalyzing material therein, a foraminous holder for sustainingand confining said body, a 'nozzle for'atomizing o'il,jmeans for oil, the. combination of a pressureetight removing said' nozzle, and said body of catalyzing materialrelatively to each other.

31. In an apparatus for hydrogenating ceptacle vprovided with a hydrogen inlet, a

supporting member therein, pervious to oil and hydrogen, a metal-containing catalytic substance supported thereupon, means' forA atomizing oill against the structure embodying said catalyzing Substanceand supportlng member, and eans for causing the oil to travel therethrough, andmeansfor caus ing the catalytic substance and the hydrogen inlet to move relatively to each other, and

means for withdrawing theltreated oil from fory hydrogenating Oil/ and into contact with successive portions of said catalyst.

33. A process of hydrogenating oil Which comprises continuously atomizing oil, continuously passing the atomized oil while at least a portion thereof is in the presence of free hydrogen through a catalyzing material. l 34. In the hydrogenation of fatty oils comprising the glycerids of unsaturated fatty esters, Athe step of passing such oils, in a non-volatile, highly attenuated condition and while at least a portion' thereof is vin the presence of hydrogen, through a catalyst maintained free from a sealing coat of saturated oil. v i

35. The step of passing an oil containing unsaturated fatty acid esters, inthe 'form of a mist of'fn'e particles, into and through Va'body ofcatalytic 1naterial, while in the presence of an atmosphere containing free hydrogen, while mechanically preventing an accumulation of a.. sealing coat of saturated fatty bodies.

36. In the hydrogenation of oils, the step of atomizing the oilsby means of steam, andpassing the fine particles thereby produced, in the presence' of hydrogen, into c'ontact with a hydrogenating catalyst.

' 37. In the hydrogenation of fatty oils, the

step of atomizing oily material against a catalyst and maintaining at least the major portion of saidv catalyst at all times substantially free from a sealing coat of hydrogenated. oily material, and maintaining at least the major portion of said catalyst below the vaporizing point of the product.

Signed at Montclairin the county of Essex and State of New Jersey this fourth day of June A. D. 1912.

Witnesses:

' A. A. WELLS,

HEDWIG VON GOEBEN.

ADoLPHUs HENRY N EY. 

